CA2261602A1 - Process for surface sizing paper and paper prepared thereby - Google Patents
Process for surface sizing paper and paper prepared thereby Download PDFInfo
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- CA2261602A1 CA2261602A1 CA002261602A CA2261602A CA2261602A1 CA 2261602 A1 CA2261602 A1 CA 2261602A1 CA 002261602 A CA002261602 A CA 002261602A CA 2261602 A CA2261602 A CA 2261602A CA 2261602 A1 CA2261602 A1 CA 2261602A1
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- Prior art keywords
- paper
- polymer
- size
- styrene
- polymer latex
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
- G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
- D21H17/43—Carboxyl groups or derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S439/00—Electrical connectors
- Y10S439/94—Electrical connectors including provision for mechanical lifting or manipulation, e.g. for vacuum lifting
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Paper (AREA)
Abstract
A process for preparing sized paper which incorporates in the paper a size composition containing polymer latex, wherein the polymer contained in the polymer latex is anionic polymer having properties selected from the group consisting of TG about - 15 ~C to about 50 ~C and acid number about 30 to about 100, and wherein the polymer latex has a zeta potential of from about -25 to about - 70 millivolts over the pH range of about 5 to about 9. A
preferred process has the steps: a) providing an aqueous pulp suspension; b) sheeting and drying the aqueous pulp suspension to obtain paper; c) treating the paper by applying to at least one surface of it the size composition containing polymer latex and starch; and d) drying the paper to obtain sized paper. Preferred anionic polymers are copolymers of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid.
preferred process has the steps: a) providing an aqueous pulp suspension; b) sheeting and drying the aqueous pulp suspension to obtain paper; c) treating the paper by applying to at least one surface of it the size composition containing polymer latex and starch; and d) drying the paper to obtain sized paper. Preferred anionic polymers are copolymers of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid.
Description
PROCESS FOR SURFACE SIZING PAPER AND PAPER PREPARED THI~eBY
Field of th~ Tnv.ontinn This invention relates to a process for sizing paper and to paper ~ re~aled by the process.
S Back~- uu,ld of the Tnventitm Surface sizing, i.e., the n l~ition of sizing agents to the surface of a paper sheet that has been at least partially dried, is widely practiced in the paper industry, particularly for printing grades. Surface sizing leads to paper with improved water holdout (sizing), improved print quality, and increased toner ~-lhP!sion The most widely used surface sizing agent is starch, which is used toenll~nce the surface charnct~?rictics of the sheet, particularly for the purposes of controlling ink fccepti~rity and porosity, and of increasing surface strength.
The growing use of ink jet printing which generally uses aqueous-based inks, has placed more string~nt requirements on paper properties, because the inks must provide printed characters with high optical density, minim~l spread (also referred to as fie~thering or bleed) and sharp or clean edges (also referred to as wicking or edge ro~l~ness). The surface charnct~ri~tics of the printing paper have been found to be a primary infl~lence on these qualities of ink jet prlntlng.
Polymer latexes are used for several functions in paper m~kin~
processes They are used as pi~nçnt binders for paper coatings, for paper salul~ls, as dispersing aids for other paper additives, and as sizing agents.
.
WO 38/43397 PCT~US98/06472 The paper co~tin~ process is completely di~ie~ll in fimrtion composition and requirements when coll,p~ed to surface sizing processes.
Paper co~stine comro~eiti~n~ have much higher viscosities than surface sizing colnro~eitionc, and thus cannot be readily applied by a size press on a typical S paper mA-.hine. Paper co~tinee conhin pi~m~nt at 3 to 20 times higher than the level of polymeric binder; whereas in a typical surface size, pi~mPntc are optional, and if used, are present at levels less than the amount of polymeric binder.
The polymer latexes that have been used for sizing are cationic l~t~xes For e~mple, U.S. Patent No. 4,434,269 discloses sizing agents for paper that are copolymers of acrylonitrile or methacrylonitrile, C,-C,2 aL4yl esters of acrylic acid and/or m~th~ ,rylic acid. The copolymers are ~m~ ified with a cationic polymeric emnleifier Co~ g N,N'-dimethylaminoethyl acrylate or methacrylate, styrene, and acrylonitrile m.~nom~rs.
U.S Patent 4,659,431 ~iecloses sizing agents for paper that are copolymers of acrylQnitlile or methacrylc-nitrile styrene, and acrylates or methA-rylates having 1 to 12 carbon atoms in the alcohol radical. The copolymers are emllleified with a cationic polymeric em~ ifi~r co~ il-g monQm~ors ccm~cieti~ of N,N'-dimethylaminoethyl acrylate or meth~clylate, styrene, and acrylQnitrile.
U.S. Patent Nos. 5,116,924 and 5,169,886 disclose sizing agent dispersions co"~ ;--g csti~niC dispersant produced from the monom~.rs:
N,N'-dimethylsminsethyl acrylate andlor methacrylate; an acrylic andlor m~th~crylic acid ester of a C~0 to C22 fatty alcohol; me~yl acrylate and/or m~th~Srylate; acrylic acid andlor meth~r,Jylic acid; and optionally butyl acrylate andlor butyl meth~cTylate and isobutyl acrylate and/or isobutyl m~th~Grylate.
CA 0226l602 l999-0l-25 W O 98/4~397 PCT/U~,8~ 172 S.~ of the TnvPntil~n A process for plep~.ng sized paper comprises incorporating in the paper a size composition cofnrricing polymer latex, wherein the polymer co~-lAi..~l inthe polymer latex is anionic polymer having prope.Lies selected from the group S c~ n~i~ting of TG about -15~C to about 50~C and acid n~llnhPr about 30 to about 100, and ~Lel~ the polymer latex has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
A process for p,~ sized paper comprises: a) providing an aqueous pulp suspension; b) ~heeting and drying the aqueous pulp suspension to obtain 10 paper; c) applying to at least one surface of the paper an aqueous size composition coTnpricing polymer latex; and d) drying the paper to obtain sized paper, wherein the polymer contAined in the polymer latex is anionic polymer having ~iope.lies sP1Pcte~l from the group concicting of TG about -15~C to about50~C and acid number about 30 to about 100, and wherein the polymer latex 15 has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
Paper surface sized by the process of the invention l,c.rO,l,~s better in ink jet p~in~ing than does paper that is the same except that it does not contain the size composition, when the printing is evAlll?te~ for at least one pl~cll~
20 selected from the group coneisting of optical density, feAth~Pring wicking, edge ronehnP,ss and bleed.
netAiled Description of thP Tnv~nti~n The polymer cont~inp~ in the polymer latex utili7e~1 in the processes of 25 this invention is charr.clr~ by glass transition temperature (TG) and acid mltnber. The polymer latex itself is charactçn7e~ in terms of its zeta potentialand particle size.
WO 98/433~7 PCT/US98/06472 The TG of the polymer is in the range of from about -15~C to about 50~C.
Preferably it is from about 5~C to about 35~C, and more preferably from about 20~C to about 30~C.
The acid n~lmber of the copolymer is from about 30 to about 100, S preferably from about 40 to about 75, and more preferably from about 45 toabout 55. Some portion of the acidic groups may be in the form of salts with aL~ali or ~ 1in~ earth metals or ~mmnni~
The zeta potential is the potential across the interf~re of solids and liquids, specifically, the potential across the diffuse layer of ions sulluul~ding a charged colloid~article which is largely responsible for colloidal stability.
Zeta potentials can be calc~ te~l from electrophoretic mobilitiPs, namely, the rates at which colloidal particles travel bel~eel~ charged electrodes placed in the dispersion, emlll~ion or s~l~pen.sion co~ g the colloidal particles. A
zeta pot~-nti~l value of zero to 10 millivolts will be an inf1ic~tor of poor stability. A zeta potential value of -10 to -19 millivolts is an in-lic~tor of some, but usually in~llfficiçnt stability. A zeta potential value of at least -20 millivolts, and preferably -25 to -40 millivolts is an in~lic~tinn of a moderatecharge with good stability. A zeta potential value of greater than -40 to -100 millivolts or more nnrm~lly in~ tes excellent stability.
In the present invention, the polymer latex has a zeta potential of from about -25 to about -70 millivolts over the pH range of about 5 to about 9.
Preferably the zeh potential is from about -35 to about -60 millivolts, and morepreferably from about -40 to about 55 millivolts. Thus, it is plefe.,ed that thecharge on the latex should be highly anionic. This corresponds to better electrostatic colloidal stability of the final product.
The average par~cle size of the polymer in the polymer latex is from about 30 to about 500 n~nometprs. Preferably it is from about 50 to about 200 n~nometers, and more preferably from about 80 to about 150 n~nom~t~rs.
W O 98/49397 PCT~US98/06472 S
Polymer latexes for use in the processes of this invention preferably contqin anionic copolymer of monomers comrricin~ styrene or substitl~ted styrene, aL~yl acrylate or mPthA ,rylate and ethylPnirq11y unsalulated carboxylic acld.
The aLkyl group of the alkyl acrylate or mP~thqcrylate preferably contains from 1 to about 12 carbon atoms. FY~mrlqry aLkyl acrylates or mPthA ,rylates are methyl mP~tL~-rylate~ ethyl acrylate, ethyl meth~crylate, propyl acrylate, butyl acrylate, butyl m~th~-rylate, 2-ethylhexyl acrylate, 2-ethylhexyl meth~~rylate, lauryl acIylate, lauryl methacrylate and ~ eS thereo~
Preferable ethylenically uns~ ed carboxylic acids for use in the invention are a"B-uns~ ated carboxylic acids. F.Yqmrles are acIylic acid, met~-~,rylic acid, maleic acid or anhydride, fi~ ric acid and it~~cnic acid.
More preferable ethylenir~lly unsalulaled carboxylic acids are acrylic acid and mPt~~~rylic acid. The most plcfel~cd ethylenically uns~ ed carboxylic acid is acrylic acid.
Preferable styrenes or sl1bstitnte(1 styrenes incl~lde styrene, a-methylstyrene and vinyl toluene. Styrene is most p~cr~..cd.
The p,cre.,ed polymer latex for use in the processes of this invention is ChromasetTM600 surface sizing tre~tm~nt available from Hercules 20 Incorporated, Wilmin~on, Delaware. This m~tçri~l has an anionic charge-(zeta potential of about -40 mV from pH 6 to 9), a total solids of 46-48% and a pH of 8to9.
A process for pr~ g sized paper comprises incorporating in the paper a size composition crl~p. ;ci,~g the polymer latex described herein. Preferably 25 the process cornrrices: (a) providing an aqueous pulp suspension; (b) sheeting and drying the aqueous pulp sucpencion to obtain paper; (c) applying to at leastone s~rfr ,e of the paper size comprising polymer latex; and (d) drying the paper to obtain sized paper. Paper sized by processes of this type is known as surface sized paper. Preferably, in surface sizing procesces the size in step (c) W O 98/43~37 PCT~US98/06472 is applied from a size press which can be any type of coating or spraying equirm~nt but most comm~-nly is a puddle, gate roller or metered blade type of size press.
The aqueous pulp snspenci~m of step (a) of the process is obtained by means well known in the art, such as known mPrhqnicql eh~mirql and s~michPmi~ql etc., pulping processec Normally, after the mPchqnical grin~ling andlor chPmirql pulping step, the pulp is washed to remove residual pulping chPtnicqlc and solubilized wood components. Either bhPq~chPd or unbleqr~h~
pulp fiber may be ~ltili7Pd in the process of this invention. Recycled pulp fibers are also suitable for use.
The ch~etin~ and d~ying of the pulp suspension is carried out by methods well known in the art. There is a variety of m?tPriqlc which in the commercial practice of mqkinE paper are cl-mmonly add to the aqueous pulp suspension before it is converted into paper, and may be used in the instant process as well. These inclllde, but are not restricted to, wet streng~ resins, intPrnql sizes, dry streng~ resins, alum, fillers, pigmpntc and dyes.
For obtaining the hi~h~st levels of surface sizing in the processes of this invention, it is p~cr~.~cd that the sheet be int~rn911y sized, that is, that sizing agents be added to the pulp suspension before it is con~el led to a paper sheet.Int~rnsl sizing helps prevent the surface size from soa-king into the sheet, thus allowing it to remain on the surface where it has m~ .n effectiveness.
The intPrnsl sizing agents enC~n~pqes any of those commrnly used at the wet end of a fine paper ~ ine. These incl~lde rosin sizes, ketene dimers and mnltim~rs, and aLkenylsuccinic anhyd~ides. The int~rnql sizes are generally used at levels of from about 0.05 wt.% to about 0.25 wt.% based on ~e weight of the dry paper sheet.
Methods and mqt~riqlc lltili7e~ for internql sizing with rosin are ~liecnsse~l by E. Strazdins in The Sizing of Paper, Second Edition, edited by W.F. Reynolds, Tappi Press, 1989, pages 1-33.
CA 0226l602 l999-0l-25 W O 98/49397 PCT/U~ 172 Suitable ketene dimers for intPrnql sizing are disclosed in U.S. Patent No. 4,279,794, United ~ine~om Patent Nos. 786,543; 903,416; 1,373,788 and 1,533,434, and in Eu~ope~ Patent Applir-q-tinn Publi~qti~ n No. 0666368 A3.
Ketene dimers are co-..~..P,~ cially available, as ~ql~arel~) and Precis~ sizing5 agents from Hercules Incol~o,al~d, Wilmin~on Delaware.
Ketene mllltimers for use in intPrnql sizes are described in: Eu.ope~
PatentAppli~qtinn Pu~licvqtionNo. 0629741Al, andinU.S. PatentNo.
5,685,815.
ALkenylsuccinic anhydrides for int~rnql sizing are disclosed in U.S.
Patent No. 4,040,900, and by C.E. Farley and R.B. Wasser in The Sizing of Paper, Second Edition, edited by W.F. Reynolds, Tappi Press, 1989, pages 51-62. A variety of aL~cenylsuccinic anhydrides is co...~ . cially available from Albemarle Col~,.alion, Baton Rouge, Lo ~i~iq~ q For surface sizing, ~e polymer latex is preferably mixed with a solution 15 of starch or starch dc.i./ali-~e prior to its application to the paper. The starch may be of any type, inchl-1in~ but not limited to oxidi~e-1 ethylated, cationic and pearl, and is preferably used in aqueous solution The typical size press starch solution preferably contains about 1 to about 20% by weight starch in wata with a pH between about 6 and 9. More 20 preferably the it cont~inC from about 3 to about 15% by weight, and most preferably 5 to about 10% by weight starch. Small amounts of other additives may be present as well, e.g., optical bri~ e ~ and d~foqrn~rs. The amount of polymer latex added to the starch solution to form the size press compound is such that the polymer solids level in the fin. l size press compound is preferably 25 from about 0.02 to about 2 wt.%. More preferably the polymer solids level will be from about 0.05 to about 1 wt.%. The final pH of the size press compound should be ,..si~ ;,,ed above about pH 7.
The size press compound is applied at the size press in an amount such that the level of polymer applied to the surface is preferably about 0.02 wt.% to CA 02261602 1999-01-2~
W O ~ 93~7 PCTAUS98/06472 -8-about 0.8 wt.% on a dry basis based on the weight of the dry sheet of paper.
More preferably the level is about 0.05 wt.% to about 0.5 wt.%, and most preferably about 0.1 wt.% to about 0.3 wt. %. The amount of starch applied to the sheet is generally about 1 to about 8 wt.%, more preferably about 2 to about5 6 wt.%, and most preferably about 3 to about 5 wt.%, on a dry basis based on the weight of the dry sheet of paper.
After app1ic~ti~n of the surface size, the sheets are dried ~ltili7ing any of the conventional dTying proce.l~es well known in the paper mq~ing art.
Surface sized paper produced by the process of this invention has 10 properties that are s~bst~nti~1ly improved over those of paper that is the same except that it does not contain the anionic polymer latex. In particular, it is found that the paper of this invention ~ rO. ..-e better in ink jet printing than does paper that is the same except that it lacks the surface size comprising polymeric latex. The ink jet printing ~,o~.lies in~ de optical density, 15 fe~th~ring wicking, edge rollghn~ss and bleed. In addition the paper of this invention demonetrates better toner adhesion than does paper l~ ing the anionic polymer latex. Moreover, it is found that the water holdout is also improved for the paper of this invention.
For the purposes of this invention ink jet printing is ev~hl~te~l on the 20 basis of the optical density of the printed characters when black ink is ~ltili7ed as well as on the amount of ink spread and the sharpness and clarity of the character edges (also known as fe~th~ring and wicking). When colored inks are used, the ev~ tion is on the basis of the edge rollghness of the characters and the amount of ink spread (also known as line growth or bleed) that is observed.
25 Toner ~1heSinn is the relative amount of white paper showing through a solid black area of toner applied by a copy machine that results for the paper being creased. Water holdout is measured by well known sizing tests such as, for eY~-nrle, the Hercules sizing test.
*rB
.
W 098/433g7 PCTAUS98/06472 _9_ This invention is illustrated by the following ç~mples, which are ~x~mpl~ty only and not intPnde~ to be limitine All percçnt~ges parts, etc., are by weight, based on the weight of the dry pulp, unless otherwise inrliC,gte-Proced lr~
7,P.ts~ p~!tPnti~l The charge on the particles of the latex was del~ ;ne~
as the zeta potential measured with a Lazer Zee~Meter model 501. This was carried out by ~lihlting 1 or 2 drops of the dispersion in 100 ml of deioni~ed water and adjusting the pH with NaOH or H2SO4.
Herrllles ~i7~ Test: An art-recognized test for measuring sizing o l~c. r.. ~.. re is the Hercules Size Test, described in Pulp and Paper Chemistry and Chemical Technology, J.P. Casey, Ed., Vol. 3, p. 1553-1554 (1981) and in TAPPI Standard T530. The Hercules Size Test del~ s the degree of water sizing obtained in paper by measuring the change in reflect~nce of the paper's surface as an aqueous solution of dye penetrates from the opposite surface side.The aqueous dye solution, e.g, n~phth-)l green dye in 1% formic acid, is cont~ine~l in a ring on the top surface of the paper, and the change in reflectance is measured rhotoeleclTicslly from the bottom surface.
Test duration is limited by choosing a convenient end point, e.g, a reduction in reflecte~ light of 20%, corresponding to 80% reflectance. A timer measulGs the time (in secon~) for the end point of the test to be re~
Longer times correlate with increased sizing petfonn~nce, i.e., resist~nce to water penetration increases. Unsized paper will typically fail at 0 secon~ls, lightly sized paper urill register times of from about 1 to about 20 seconds, moderately sized paper from about 21 to about 150 seconds, and hard sized paper from about 151 to about 2,000 seconds.
poly~ner Gl~c Tr~ncition Te..~ e (T~): Det~ ed by dirrere~llial sc~ g calorimetry on dry polymer i~sl~ted from the latex at a heating rate of W 098/49397 PCT~US98/06472 20~C/...;...~Ie The inflection point of the If ..pc- ;~ c vs. heat capacity curve is taken as the TG
Tnk Jet ~ Fv~ ti~m Ink jet printing was tested with a Hewlett Packard Deskjet 560C printer. A Hewlett Packard 3.4 test pattern and method were~ used to rate the quality of the prin~in~
Before testing the paper was cQn~litiQn~l at 23~ C and 50% relative hllmi~lity for a ...;~ -.. of one (1) day.
A Fv~ tinn of Rl~t~Tnk Print Q-l~lity Optical Density - An optical ~IPn~it~mPtpr was placed over the black test rec~le on the printed sheet, and the optical density for black was recorded. This was repeated on di~relll areas of the rect~n~le for a total of 6 r~ ~in~e Black Ink Spread (FP~th~rin~) - Black ink spread is the tPn~ncy for the ink to spread out from the print area. Using the m~ er, areas of the test pattern co~ictin~ of rows of the letter "E" were eY~rnined and the print quality was co~ ed with standard ~Y~mrles of acceptable, good and nn~ccept~ble feathering. Specific areas that were elr~mined were:
degree of rounding of the square ends of the letter; amount of separation between the center stroke and the right ends of the letter, general breadth of the lines, etc. Similar inspection of line growth was made using the vertical and h~. ;,n..~l black lines in the test p~ttern Black Edge Ron~hness (Wicking) - Black edge ro~ h~ess or wicking is the tçndPncy for the ink to bleed away from the print area along a fiber or one direction, c~ n~ rough edges, even long "spidery" lines on the p~iphery of the print area. Using the ma~ifiçr, all areas of the test pattern where black lines are printed against a white backg~oulld were j llf ~l .
W O 98/49397 PCT~US98/06472 and co.--yA~d with the standard eY~Amp1es of accepPble good and lmA~ceptAble wicking.
R~. Fv~ tinn of Color Print Q~-Alit,y Optical Density -The optical ~ c;l....... rtf r was positi~nf ~l over the S co,.-l)osile black rect-Angle on the printed sheet, and the black optical density n~lmber was ~ecGl-led. The comrQsitÇ black print con~i~ed of a coml~inA-ti~ n of cyan, magf ntA~ and yellow inks. The procedure was r~pealed on di~e.~- nl areas of the rect~ngle for a total of 6 llePding~
which were averaged and reported as comrosite black optical density.
Color -Color Edge Rol~hness - Color-color edge rol~hn~ss measures the ro~lehness of lines in areas where two colors overlap. Areas of ~e test pattern where composite black and yellow areas overlap were eY7 minf ~ with a ma~ifier and co.-.~ ed with standard examples to judge whether the print quality was acceptable, good or ~m~ccept~ble.
Color-Color Line Growth - Color-color line growth çy3tnin~s the size of printed fealul~,s of one color touching or overl~r~ing another color versus the in~ntle~l size. A m~Agnifier was used to ex~mine the overlapping color text areas of the test pattern and to COnl~);~e them with standard eY~n~rlf s as acceptable, good or non-acceptable. Specifically, the size of cnmrositf black characters on a yellow background was P,YAmine~l To-nf~r A~1hf~cinn: Relative toner ~ esinn is the relative amount of white paper showing through a solid black area of toner, applied by a copy mA~~ine, that results from the paper being creased. For the test, the paper was creased in a controlled fashion (toner on the inside of the crease), was unfolded, and then the loose toner was removed in a reproducible ~nAl~l~f ~ . The l~ercç~ ge of the crack area from which toner was lost was esl;...~te~ by microscopic or optical density measurement W O 98/49397 PCT~US98/06472 of the crack and su~ ng areas of toner, and reported as the toner adhesion value. Thus, a smaller value means that less toner is lost thus in/li~ ~in~ greater toner ~lh~sion F,Yanl,ple 1 S This eY~n~rle illusLlales surface sizing with ~niQnic latex, Chromaset~600, sll~ce sizing l~ nf --~ available from Hercules Inco~ aled, Wilmin~nn, DE. The latex (47% solids) had a zeta potential of a~lo,~;...~tely -40 mV from pH 6 to 9, and an average particle size of approx;n-qtely 100 nm. Polymer isolated from the latex by drying had TG of appro~imst~Ply 25~C.
Paper was prep~ed on a commercial paper m~~lline using the following procedures and con~litic-ne.
~atP.r~
Paper at a basis weight of 75 kg/1000 m2 was prepa~ed from a combination of hard wood and soft wood pulps. The paper was sized intPrn~lly with rosin size and alum and containPl1 clay as a filler. The paper was dried before the size press to about 3% moisture.
A starch solution co~ g 8.5% ammonium persulfate converted starch by weight, to which varying amounts of polymer latex were added was used for application at the size press. Paper was surface sized with starch alone and with acombination of starch and latex:
Starch Level Latex Level ~n~le (wt.% nn dly P~PO (wt.% O~ y p~per) A 5 0 (starchonly) B 5 o.os The product sl~rface sized paper was ev~ te~l for sizing using the Hercules Size Test (HST), and for ink jet print quality, i.e., optical density, WO 98/49397 PCT~US98106472 fe,sthPrin~ and wicking using black and colored inks. Relative toner ~hPcion was also ~lele- ...;.-e~l The results were as follows:
HST Rl~rk Tn1 ~m~ple ~ecln~ Optir~l T~Pnci~ Fe~thPri~ Wir~
A 167 1.34 acceptable acceptable B 266 1.39 acceptable good Colored Tnk CompositeBlack Color-to Color Color-to-Color ~,snr~pleOptir~l n~ncity F ~ e Ro~hn~cc T,ine ~rowth A 0.87 acceptable ;~ccept~le B 0.88 acceptable good S~mple Rel~tive Tonrr ~lhPcion The data in~lir,?te that the paper surface sized with polymer latex by the process of the invention exhibits nl~rke-lly better perform~nce in black ink jetprintinf~ somewhat better perfQrmsnr,e in color ink jet printing, and considerably ~ro~d perfc rm~nce in relative toner r lh~Sion than does paper 20 sized with starch alone.
FY~n~PIe ~
A polymer latex available as Carboset~)GA1086 was obtained from B.F.
Goodrich Co., Cleveland, Ohio. Dry polymer isolated from the latex (49%
solids) was analyzed and found to comprise the monomers styrene, 2-W O 98/43397 PCT~US98/06472 ethylhexyl acrylate and acrylic acid. The polymer had acid number 50, TG of 12~C and zeta potential from pH 5 to 9 that ranged from -29 to -35 millivolts.
A size press solution at pH 7.5 was pltp~cd co"~ g 7.3 wt.% of oxi~1i7ç~1 starch, 0.01% of an oil based defoamer and a low level of a S be~ iazole based biocide. The polymer latex was added at a level to provide 0.30 wt.% polymer in the size press solllti~n The size composition was applied from the size press of a commercial paper m~.hine in a quantity that provided a level of 0.13% by weight of the polymer in the dry paper.
The paper eYhibited improved water hold out (sizing as measured by the 10 Hercules Sizing Test) and improved ink jet printing quality. The final black and color ink jet print quality was acceptable-to-good based on Hewlett Packard standards.
After 10 hours of contin-l~l use on the paper m~~llinç, deposits in the m~ ine were observed and traced to the use of the polymer latex. The 15 deposits con~ieted of a slight build up of material at the screens where excess size press solution f~ d from the size press to the feed tank. This instability in-lic~tçs that the zeta potential was not in the most ~lcf~.~cd range of about -40 to -55 millivolts for best m~ ine stability.
It is not int~nded that the elr~mrles pres~nted here should be construed 20 to limit the invention, but rather they are sllbmitted to illustrate some of the specific embo~lim~nte of the invention. Various modific~tinne and vanations of the present invention can be made without de~ g from the scope of the nppen~le~ claims.
Field of th~ Tnv.ontinn This invention relates to a process for sizing paper and to paper ~ re~aled by the process.
S Back~- uu,ld of the Tnventitm Surface sizing, i.e., the n l~ition of sizing agents to the surface of a paper sheet that has been at least partially dried, is widely practiced in the paper industry, particularly for printing grades. Surface sizing leads to paper with improved water holdout (sizing), improved print quality, and increased toner ~-lhP!sion The most widely used surface sizing agent is starch, which is used toenll~nce the surface charnct~?rictics of the sheet, particularly for the purposes of controlling ink fccepti~rity and porosity, and of increasing surface strength.
The growing use of ink jet printing which generally uses aqueous-based inks, has placed more string~nt requirements on paper properties, because the inks must provide printed characters with high optical density, minim~l spread (also referred to as fie~thering or bleed) and sharp or clean edges (also referred to as wicking or edge ro~l~ness). The surface charnct~ri~tics of the printing paper have been found to be a primary infl~lence on these qualities of ink jet prlntlng.
Polymer latexes are used for several functions in paper m~kin~
processes They are used as pi~nçnt binders for paper coatings, for paper salul~ls, as dispersing aids for other paper additives, and as sizing agents.
.
WO 38/43397 PCT~US98/06472 The paper co~tin~ process is completely di~ie~ll in fimrtion composition and requirements when coll,p~ed to surface sizing processes.
Paper co~stine comro~eiti~n~ have much higher viscosities than surface sizing colnro~eitionc, and thus cannot be readily applied by a size press on a typical S paper mA-.hine. Paper co~tinee conhin pi~m~nt at 3 to 20 times higher than the level of polymeric binder; whereas in a typical surface size, pi~mPntc are optional, and if used, are present at levels less than the amount of polymeric binder.
The polymer latexes that have been used for sizing are cationic l~t~xes For e~mple, U.S. Patent No. 4,434,269 discloses sizing agents for paper that are copolymers of acrylonitrile or methacrylonitrile, C,-C,2 aL4yl esters of acrylic acid and/or m~th~ ,rylic acid. The copolymers are ~m~ ified with a cationic polymeric emnleifier Co~ g N,N'-dimethylaminoethyl acrylate or methacrylate, styrene, and acrylonitrile m.~nom~rs.
U.S Patent 4,659,431 ~iecloses sizing agents for paper that are copolymers of acrylQnitlile or methacrylc-nitrile styrene, and acrylates or methA-rylates having 1 to 12 carbon atoms in the alcohol radical. The copolymers are emllleified with a cationic polymeric em~ ifi~r co~ il-g monQm~ors ccm~cieti~ of N,N'-dimethylaminoethyl acrylate or meth~clylate, styrene, and acrylQnitrile.
U.S. Patent Nos. 5,116,924 and 5,169,886 disclose sizing agent dispersions co"~ ;--g csti~niC dispersant produced from the monom~.rs:
N,N'-dimethylsminsethyl acrylate andlor methacrylate; an acrylic andlor m~th~crylic acid ester of a C~0 to C22 fatty alcohol; me~yl acrylate and/or m~th~Srylate; acrylic acid andlor meth~r,Jylic acid; and optionally butyl acrylate andlor butyl meth~cTylate and isobutyl acrylate and/or isobutyl m~th~Grylate.
CA 0226l602 l999-0l-25 W O 98/4~397 PCT/U~,8~ 172 S.~ of the TnvPntil~n A process for plep~.ng sized paper comprises incorporating in the paper a size composition cofnrricing polymer latex, wherein the polymer co~-lAi..~l inthe polymer latex is anionic polymer having prope.Lies selected from the group S c~ n~i~ting of TG about -15~C to about 50~C and acid n~llnhPr about 30 to about 100, and ~Lel~ the polymer latex has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
A process for p,~ sized paper comprises: a) providing an aqueous pulp suspension; b) ~heeting and drying the aqueous pulp suspension to obtain 10 paper; c) applying to at least one surface of the paper an aqueous size composition coTnpricing polymer latex; and d) drying the paper to obtain sized paper, wherein the polymer contAined in the polymer latex is anionic polymer having ~iope.lies sP1Pcte~l from the group concicting of TG about -15~C to about50~C and acid number about 30 to about 100, and wherein the polymer latex 15 has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
Paper surface sized by the process of the invention l,c.rO,l,~s better in ink jet p~in~ing than does paper that is the same except that it does not contain the size composition, when the printing is evAlll?te~ for at least one pl~cll~
20 selected from the group coneisting of optical density, feAth~Pring wicking, edge ronehnP,ss and bleed.
netAiled Description of thP Tnv~nti~n The polymer cont~inp~ in the polymer latex utili7e~1 in the processes of 25 this invention is charr.clr~ by glass transition temperature (TG) and acid mltnber. The polymer latex itself is charactçn7e~ in terms of its zeta potentialand particle size.
WO 98/433~7 PCT/US98/06472 The TG of the polymer is in the range of from about -15~C to about 50~C.
Preferably it is from about 5~C to about 35~C, and more preferably from about 20~C to about 30~C.
The acid n~lmber of the copolymer is from about 30 to about 100, S preferably from about 40 to about 75, and more preferably from about 45 toabout 55. Some portion of the acidic groups may be in the form of salts with aL~ali or ~ 1in~ earth metals or ~mmnni~
The zeta potential is the potential across the interf~re of solids and liquids, specifically, the potential across the diffuse layer of ions sulluul~ding a charged colloid~article which is largely responsible for colloidal stability.
Zeta potentials can be calc~ te~l from electrophoretic mobilitiPs, namely, the rates at which colloidal particles travel bel~eel~ charged electrodes placed in the dispersion, emlll~ion or s~l~pen.sion co~ g the colloidal particles. A
zeta pot~-nti~l value of zero to 10 millivolts will be an inf1ic~tor of poor stability. A zeta potential value of -10 to -19 millivolts is an in-lic~tor of some, but usually in~llfficiçnt stability. A zeta potential value of at least -20 millivolts, and preferably -25 to -40 millivolts is an in~lic~tinn of a moderatecharge with good stability. A zeta potential value of greater than -40 to -100 millivolts or more nnrm~lly in~ tes excellent stability.
In the present invention, the polymer latex has a zeta potential of from about -25 to about -70 millivolts over the pH range of about 5 to about 9.
Preferably the zeh potential is from about -35 to about -60 millivolts, and morepreferably from about -40 to about 55 millivolts. Thus, it is plefe.,ed that thecharge on the latex should be highly anionic. This corresponds to better electrostatic colloidal stability of the final product.
The average par~cle size of the polymer in the polymer latex is from about 30 to about 500 n~nometprs. Preferably it is from about 50 to about 200 n~nometers, and more preferably from about 80 to about 150 n~nom~t~rs.
W O 98/49397 PCT~US98/06472 S
Polymer latexes for use in the processes of this invention preferably contqin anionic copolymer of monomers comrricin~ styrene or substitl~ted styrene, aL~yl acrylate or mPthA ,rylate and ethylPnirq11y unsalulated carboxylic acld.
The aLkyl group of the alkyl acrylate or mP~thqcrylate preferably contains from 1 to about 12 carbon atoms. FY~mrlqry aLkyl acrylates or mPthA ,rylates are methyl mP~tL~-rylate~ ethyl acrylate, ethyl meth~crylate, propyl acrylate, butyl acrylate, butyl m~th~-rylate, 2-ethylhexyl acrylate, 2-ethylhexyl meth~~rylate, lauryl acIylate, lauryl methacrylate and ~ eS thereo~
Preferable ethylenically uns~ ed carboxylic acids for use in the invention are a"B-uns~ ated carboxylic acids. F.Yqmrles are acIylic acid, met~-~,rylic acid, maleic acid or anhydride, fi~ ric acid and it~~cnic acid.
More preferable ethylenir~lly unsalulaled carboxylic acids are acrylic acid and mPt~~~rylic acid. The most plcfel~cd ethylenically uns~ ed carboxylic acid is acrylic acid.
Preferable styrenes or sl1bstitnte(1 styrenes incl~lde styrene, a-methylstyrene and vinyl toluene. Styrene is most p~cr~..cd.
The p,cre.,ed polymer latex for use in the processes of this invention is ChromasetTM600 surface sizing tre~tm~nt available from Hercules 20 Incorporated, Wilmin~on, Delaware. This m~tçri~l has an anionic charge-(zeta potential of about -40 mV from pH 6 to 9), a total solids of 46-48% and a pH of 8to9.
A process for pr~ g sized paper comprises incorporating in the paper a size composition crl~p. ;ci,~g the polymer latex described herein. Preferably 25 the process cornrrices: (a) providing an aqueous pulp suspension; (b) sheeting and drying the aqueous pulp sucpencion to obtain paper; (c) applying to at leastone s~rfr ,e of the paper size comprising polymer latex; and (d) drying the paper to obtain sized paper. Paper sized by processes of this type is known as surface sized paper. Preferably, in surface sizing procesces the size in step (c) W O 98/43~37 PCT~US98/06472 is applied from a size press which can be any type of coating or spraying equirm~nt but most comm~-nly is a puddle, gate roller or metered blade type of size press.
The aqueous pulp snspenci~m of step (a) of the process is obtained by means well known in the art, such as known mPrhqnicql eh~mirql and s~michPmi~ql etc., pulping processec Normally, after the mPchqnical grin~ling andlor chPmirql pulping step, the pulp is washed to remove residual pulping chPtnicqlc and solubilized wood components. Either bhPq~chPd or unbleqr~h~
pulp fiber may be ~ltili7Pd in the process of this invention. Recycled pulp fibers are also suitable for use.
The ch~etin~ and d~ying of the pulp suspension is carried out by methods well known in the art. There is a variety of m?tPriqlc which in the commercial practice of mqkinE paper are cl-mmonly add to the aqueous pulp suspension before it is converted into paper, and may be used in the instant process as well. These inclllde, but are not restricted to, wet streng~ resins, intPrnql sizes, dry streng~ resins, alum, fillers, pigmpntc and dyes.
For obtaining the hi~h~st levels of surface sizing in the processes of this invention, it is p~cr~.~cd that the sheet be int~rn911y sized, that is, that sizing agents be added to the pulp suspension before it is con~el led to a paper sheet.Int~rnsl sizing helps prevent the surface size from soa-king into the sheet, thus allowing it to remain on the surface where it has m~ .n effectiveness.
The intPrnsl sizing agents enC~n~pqes any of those commrnly used at the wet end of a fine paper ~ ine. These incl~lde rosin sizes, ketene dimers and mnltim~rs, and aLkenylsuccinic anhyd~ides. The int~rnql sizes are generally used at levels of from about 0.05 wt.% to about 0.25 wt.% based on ~e weight of the dry paper sheet.
Methods and mqt~riqlc lltili7e~ for internql sizing with rosin are ~liecnsse~l by E. Strazdins in The Sizing of Paper, Second Edition, edited by W.F. Reynolds, Tappi Press, 1989, pages 1-33.
CA 0226l602 l999-0l-25 W O 98/49397 PCT/U~ 172 Suitable ketene dimers for intPrnql sizing are disclosed in U.S. Patent No. 4,279,794, United ~ine~om Patent Nos. 786,543; 903,416; 1,373,788 and 1,533,434, and in Eu~ope~ Patent Applir-q-tinn Publi~qti~ n No. 0666368 A3.
Ketene dimers are co-..~..P,~ cially available, as ~ql~arel~) and Precis~ sizing5 agents from Hercules Incol~o,al~d, Wilmin~on Delaware.
Ketene mllltimers for use in intPrnql sizes are described in: Eu.ope~
PatentAppli~qtinn Pu~licvqtionNo. 0629741Al, andinU.S. PatentNo.
5,685,815.
ALkenylsuccinic anhydrides for int~rnql sizing are disclosed in U.S.
Patent No. 4,040,900, and by C.E. Farley and R.B. Wasser in The Sizing of Paper, Second Edition, edited by W.F. Reynolds, Tappi Press, 1989, pages 51-62. A variety of aL~cenylsuccinic anhydrides is co...~ . cially available from Albemarle Col~,.alion, Baton Rouge, Lo ~i~iq~ q For surface sizing, ~e polymer latex is preferably mixed with a solution 15 of starch or starch dc.i./ali-~e prior to its application to the paper. The starch may be of any type, inchl-1in~ but not limited to oxidi~e-1 ethylated, cationic and pearl, and is preferably used in aqueous solution The typical size press starch solution preferably contains about 1 to about 20% by weight starch in wata with a pH between about 6 and 9. More 20 preferably the it cont~inC from about 3 to about 15% by weight, and most preferably 5 to about 10% by weight starch. Small amounts of other additives may be present as well, e.g., optical bri~ e ~ and d~foqrn~rs. The amount of polymer latex added to the starch solution to form the size press compound is such that the polymer solids level in the fin. l size press compound is preferably 25 from about 0.02 to about 2 wt.%. More preferably the polymer solids level will be from about 0.05 to about 1 wt.%. The final pH of the size press compound should be ,..si~ ;,,ed above about pH 7.
The size press compound is applied at the size press in an amount such that the level of polymer applied to the surface is preferably about 0.02 wt.% to CA 02261602 1999-01-2~
W O ~ 93~7 PCTAUS98/06472 -8-about 0.8 wt.% on a dry basis based on the weight of the dry sheet of paper.
More preferably the level is about 0.05 wt.% to about 0.5 wt.%, and most preferably about 0.1 wt.% to about 0.3 wt. %. The amount of starch applied to the sheet is generally about 1 to about 8 wt.%, more preferably about 2 to about5 6 wt.%, and most preferably about 3 to about 5 wt.%, on a dry basis based on the weight of the dry sheet of paper.
After app1ic~ti~n of the surface size, the sheets are dried ~ltili7ing any of the conventional dTying proce.l~es well known in the paper mq~ing art.
Surface sized paper produced by the process of this invention has 10 properties that are s~bst~nti~1ly improved over those of paper that is the same except that it does not contain the anionic polymer latex. In particular, it is found that the paper of this invention ~ rO. ..-e better in ink jet printing than does paper that is the same except that it lacks the surface size comprising polymeric latex. The ink jet printing ~,o~.lies in~ de optical density, 15 fe~th~ring wicking, edge rollghn~ss and bleed. In addition the paper of this invention demonetrates better toner adhesion than does paper l~ ing the anionic polymer latex. Moreover, it is found that the water holdout is also improved for the paper of this invention.
For the purposes of this invention ink jet printing is ev~hl~te~l on the 20 basis of the optical density of the printed characters when black ink is ~ltili7ed as well as on the amount of ink spread and the sharpness and clarity of the character edges (also known as fe~th~ring and wicking). When colored inks are used, the ev~ tion is on the basis of the edge rollghness of the characters and the amount of ink spread (also known as line growth or bleed) that is observed.
25 Toner ~1heSinn is the relative amount of white paper showing through a solid black area of toner applied by a copy machine that results for the paper being creased. Water holdout is measured by well known sizing tests such as, for eY~-nrle, the Hercules sizing test.
*rB
.
W 098/433g7 PCTAUS98/06472 _9_ This invention is illustrated by the following ç~mples, which are ~x~mpl~ty only and not intPnde~ to be limitine All percçnt~ges parts, etc., are by weight, based on the weight of the dry pulp, unless otherwise inrliC,gte-Proced lr~
7,P.ts~ p~!tPnti~l The charge on the particles of the latex was del~ ;ne~
as the zeta potential measured with a Lazer Zee~Meter model 501. This was carried out by ~lihlting 1 or 2 drops of the dispersion in 100 ml of deioni~ed water and adjusting the pH with NaOH or H2SO4.
Herrllles ~i7~ Test: An art-recognized test for measuring sizing o l~c. r.. ~.. re is the Hercules Size Test, described in Pulp and Paper Chemistry and Chemical Technology, J.P. Casey, Ed., Vol. 3, p. 1553-1554 (1981) and in TAPPI Standard T530. The Hercules Size Test del~ s the degree of water sizing obtained in paper by measuring the change in reflect~nce of the paper's surface as an aqueous solution of dye penetrates from the opposite surface side.The aqueous dye solution, e.g, n~phth-)l green dye in 1% formic acid, is cont~ine~l in a ring on the top surface of the paper, and the change in reflectance is measured rhotoeleclTicslly from the bottom surface.
Test duration is limited by choosing a convenient end point, e.g, a reduction in reflecte~ light of 20%, corresponding to 80% reflectance. A timer measulGs the time (in secon~) for the end point of the test to be re~
Longer times correlate with increased sizing petfonn~nce, i.e., resist~nce to water penetration increases. Unsized paper will typically fail at 0 secon~ls, lightly sized paper urill register times of from about 1 to about 20 seconds, moderately sized paper from about 21 to about 150 seconds, and hard sized paper from about 151 to about 2,000 seconds.
poly~ner Gl~c Tr~ncition Te..~ e (T~): Det~ ed by dirrere~llial sc~ g calorimetry on dry polymer i~sl~ted from the latex at a heating rate of W 098/49397 PCT~US98/06472 20~C/...;...~Ie The inflection point of the If ..pc- ;~ c vs. heat capacity curve is taken as the TG
Tnk Jet ~ Fv~ ti~m Ink jet printing was tested with a Hewlett Packard Deskjet 560C printer. A Hewlett Packard 3.4 test pattern and method were~ used to rate the quality of the prin~in~
Before testing the paper was cQn~litiQn~l at 23~ C and 50% relative hllmi~lity for a ...;~ -.. of one (1) day.
A Fv~ tinn of Rl~t~Tnk Print Q-l~lity Optical Density - An optical ~IPn~it~mPtpr was placed over the black test rec~le on the printed sheet, and the optical density for black was recorded. This was repeated on di~relll areas of the rect~n~le for a total of 6 r~ ~in~e Black Ink Spread (FP~th~rin~) - Black ink spread is the tPn~ncy for the ink to spread out from the print area. Using the m~ er, areas of the test pattern co~ictin~ of rows of the letter "E" were eY~rnined and the print quality was co~ ed with standard ~Y~mrles of acceptable, good and nn~ccept~ble feathering. Specific areas that were elr~mined were:
degree of rounding of the square ends of the letter; amount of separation between the center stroke and the right ends of the letter, general breadth of the lines, etc. Similar inspection of line growth was made using the vertical and h~. ;,n..~l black lines in the test p~ttern Black Edge Ron~hness (Wicking) - Black edge ro~ h~ess or wicking is the tçndPncy for the ink to bleed away from the print area along a fiber or one direction, c~ n~ rough edges, even long "spidery" lines on the p~iphery of the print area. Using the ma~ifiçr, all areas of the test pattern where black lines are printed against a white backg~oulld were j llf ~l .
W O 98/49397 PCT~US98/06472 and co.--yA~d with the standard eY~Amp1es of accepPble good and lmA~ceptAble wicking.
R~. Fv~ tinn of Color Print Q~-Alit,y Optical Density -The optical ~ c;l....... rtf r was positi~nf ~l over the S co,.-l)osile black rect-Angle on the printed sheet, and the black optical density n~lmber was ~ecGl-led. The comrQsitÇ black print con~i~ed of a coml~inA-ti~ n of cyan, magf ntA~ and yellow inks. The procedure was r~pealed on di~e.~- nl areas of the rect~ngle for a total of 6 llePding~
which were averaged and reported as comrosite black optical density.
Color -Color Edge Rol~hness - Color-color edge rol~hn~ss measures the ro~lehness of lines in areas where two colors overlap. Areas of ~e test pattern where composite black and yellow areas overlap were eY7 minf ~ with a ma~ifier and co.-.~ ed with standard examples to judge whether the print quality was acceptable, good or ~m~ccept~ble.
Color-Color Line Growth - Color-color line growth çy3tnin~s the size of printed fealul~,s of one color touching or overl~r~ing another color versus the in~ntle~l size. A m~Agnifier was used to ex~mine the overlapping color text areas of the test pattern and to COnl~);~e them with standard eY~n~rlf s as acceptable, good or non-acceptable. Specifically, the size of cnmrositf black characters on a yellow background was P,YAmine~l To-nf~r A~1hf~cinn: Relative toner ~ esinn is the relative amount of white paper showing through a solid black area of toner, applied by a copy mA~~ine, that results from the paper being creased. For the test, the paper was creased in a controlled fashion (toner on the inside of the crease), was unfolded, and then the loose toner was removed in a reproducible ~nAl~l~f ~ . The l~ercç~ ge of the crack area from which toner was lost was esl;...~te~ by microscopic or optical density measurement W O 98/49397 PCT~US98/06472 of the crack and su~ ng areas of toner, and reported as the toner adhesion value. Thus, a smaller value means that less toner is lost thus in/li~ ~in~ greater toner ~lh~sion F,Yanl,ple 1 S This eY~n~rle illusLlales surface sizing with ~niQnic latex, Chromaset~600, sll~ce sizing l~ nf --~ available from Hercules Inco~ aled, Wilmin~nn, DE. The latex (47% solids) had a zeta potential of a~lo,~;...~tely -40 mV from pH 6 to 9, and an average particle size of approx;n-qtely 100 nm. Polymer isolated from the latex by drying had TG of appro~imst~Ply 25~C.
Paper was prep~ed on a commercial paper m~~lline using the following procedures and con~litic-ne.
~atP.r~
Paper at a basis weight of 75 kg/1000 m2 was prepa~ed from a combination of hard wood and soft wood pulps. The paper was sized intPrn~lly with rosin size and alum and containPl1 clay as a filler. The paper was dried before the size press to about 3% moisture.
A starch solution co~ g 8.5% ammonium persulfate converted starch by weight, to which varying amounts of polymer latex were added was used for application at the size press. Paper was surface sized with starch alone and with acombination of starch and latex:
Starch Level Latex Level ~n~le (wt.% nn dly P~PO (wt.% O~ y p~per) A 5 0 (starchonly) B 5 o.os The product sl~rface sized paper was ev~ te~l for sizing using the Hercules Size Test (HST), and for ink jet print quality, i.e., optical density, WO 98/49397 PCT~US98106472 fe,sthPrin~ and wicking using black and colored inks. Relative toner ~hPcion was also ~lele- ...;.-e~l The results were as follows:
HST Rl~rk Tn1 ~m~ple ~ecln~ Optir~l T~Pnci~ Fe~thPri~ Wir~
A 167 1.34 acceptable acceptable B 266 1.39 acceptable good Colored Tnk CompositeBlack Color-to Color Color-to-Color ~,snr~pleOptir~l n~ncity F ~ e Ro~hn~cc T,ine ~rowth A 0.87 acceptable ;~ccept~le B 0.88 acceptable good S~mple Rel~tive Tonrr ~lhPcion The data in~lir,?te that the paper surface sized with polymer latex by the process of the invention exhibits nl~rke-lly better perform~nce in black ink jetprintinf~ somewhat better perfQrmsnr,e in color ink jet printing, and considerably ~ro~d perfc rm~nce in relative toner r lh~Sion than does paper 20 sized with starch alone.
FY~n~PIe ~
A polymer latex available as Carboset~)GA1086 was obtained from B.F.
Goodrich Co., Cleveland, Ohio. Dry polymer isolated from the latex (49%
solids) was analyzed and found to comprise the monomers styrene, 2-W O 98/43397 PCT~US98/06472 ethylhexyl acrylate and acrylic acid. The polymer had acid number 50, TG of 12~C and zeta potential from pH 5 to 9 that ranged from -29 to -35 millivolts.
A size press solution at pH 7.5 was pltp~cd co"~ g 7.3 wt.% of oxi~1i7ç~1 starch, 0.01% of an oil based defoamer and a low level of a S be~ iazole based biocide. The polymer latex was added at a level to provide 0.30 wt.% polymer in the size press solllti~n The size composition was applied from the size press of a commercial paper m~.hine in a quantity that provided a level of 0.13% by weight of the polymer in the dry paper.
The paper eYhibited improved water hold out (sizing as measured by the 10 Hercules Sizing Test) and improved ink jet printing quality. The final black and color ink jet print quality was acceptable-to-good based on Hewlett Packard standards.
After 10 hours of contin-l~l use on the paper m~~llinç, deposits in the m~ ine were observed and traced to the use of the polymer latex. The 15 deposits con~ieted of a slight build up of material at the screens where excess size press solution f~ d from the size press to the feed tank. This instability in-lic~tçs that the zeta potential was not in the most ~lcf~.~cd range of about -40 to -55 millivolts for best m~ ine stability.
It is not int~nded that the elr~mrles pres~nted here should be construed 20 to limit the invention, but rather they are sllbmitted to illustrate some of the specific embo~lim~nte of the invention. Various modific~tinne and vanations of the present invention can be made without de~ g from the scope of the nppen~le~ claims.
Claims (47)
1. A process for preparing sized paper comprising incorporating in the paper a size composition comprising polymer latex wherein the polymer contained in the polymer latex is anionic polymer having properties selected from the group consisting of T G about -15°C to about 50°C and acid number about 30 to about 100, and wherein the polymer latex has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
2. The process of claim 1 wherein the polymer latex has an average particle size of from about 30 to about 500 nanometers.
3. The process of claim 1 wherein the anionic polymer has properties selected from the group consisting of T G about 5°C to about 35°C and acid number about 40 to about 75, and wherein the polymer latex has a zeta potential of about -35 to about -60 millivolts over the pH range of about 5 to about 9.
4. The process of claim 1 wherein the anionic polymer has properties selected from the group consisting of T G about 20°C to about 30°C
and acid number about 45 to about 55, and wherein the polymer latex has a zeta potential of about -40 to about -50 millivolts over the pH range of about 5 to about 9.
and acid number about 45 to about 55, and wherein the polymer latex has a zeta potential of about -40 to about -50 millivolts over the pH range of about 5 to about 9.
5. The process of claim 1 wherein the anionic polymer has a T G
about -15°C to 50°C and an acid number about 30 to about 100, and wherein the polymer latex has a zeta potential of about -25 to about -70 millivolts overthe pH range of about 5 to about 9.
about -15°C to 50°C and an acid number about 30 to about 100, and wherein the polymer latex has a zeta potential of about -25 to about -70 millivolts overthe pH range of about 5 to about 9.
6. The process of claim 1 wherein the sizing is surface sizing.
7. The process of claim 1 wherein the polymer latex is ChromasetTM600 surface sizing treatment.
8. The process of claim 1 wherein the polymer contained in said polymer latex is an anionic copolymer of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid.
9. The process of claim 1 wherein the polymer contained in said polymer latex is an anionic copolymer of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid, wherein the styrene or substituted styrene is selected from thegroup consisting of styrene, .alpha.-methylstyrene, vinyl toluene and mixtures thereof, wherein the alkyl group of the alkyl acrylate or methacrylate contains from 1 to about 12 carbon atoms and wherein the ethylenically unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid and mixtures thereof.
10. The process of claim 1 wherein the polymer contained in said polymer latex is an anionic copolymer of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid, wherein the styrene or substituted styrene is styrene, wherein the alkyl acrylate or methacrylate is selected from the group consisting of methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate and mixtures thereof and wherein the ethylenically unsaturated carboxylic acid is selected from the group consisting of acrylic acid and methacrylic acid.
11. A process for preparing sized paper comprising:
a) providing an aqueous pulp suspension;
b) sheeting and drying the aqueous pulp suspension to obtain paper;
c) applying to at least one surface of the paper an aqueous size composition comprising polymer latex; and d) drying the paper to obtain sized paper, wherein the polymer contained in the polymer latex is anionic polymer having properties selected from the group consisting of T G about -15°C to about 50°C and acid number about 30 to about 100, and wherein the polymerlatex has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
a) providing an aqueous pulp suspension;
b) sheeting and drying the aqueous pulp suspension to obtain paper;
c) applying to at least one surface of the paper an aqueous size composition comprising polymer latex; and d) drying the paper to obtain sized paper, wherein the polymer contained in the polymer latex is anionic polymer having properties selected from the group consisting of T G about -15°C to about 50°C and acid number about 30 to about 100, and wherein the polymerlatex has a zeta potential of about -25 to about -70 millivolts over the pH range of about 5 to about 9.
12. The process of claim 11 wherein the sizing is surface sizing.
13. The process of claim 11 wherein the polymer latex has an average particle size of from about 30 to about 500 nanometers.
14. The process of claim 11 wherein the anionic polymer has properties selected from the group consisting of T G about 5°C to about 35°C and acid number about 40 to about 75, and wherein the polymer latex has a zeta potential of about -35 to about -60 millivolts over the pH range of about 5 to about 9.
15. The process of claim 11 wherein the anionic polymer has properties selected from the group consisting of T G about 20°C to about 30°C
and acid number about 45 to about 55, and wherein the polymer latex has a zeta potential of about -40 to about -55 millivolts over the pH range of about 5 to about 9.
and acid number about 45 to about 55, and wherein the polymer latex has a zeta potential of about -40 to about -55 millivolts over the pH range of about 5 to about 9.
16. The process of claim 11 wherein the anionic polymer has a T G
about -15°C to 50°C and an acid number about 30 to about 100, and wherein the polymer latex has a zeta potential of about -25 to about -70 millivolts overthe pH range of about 5 to about 9.
about -15°C to 50°C and an acid number about 30 to about 100, and wherein the polymer latex has a zeta potential of about -25 to about -70 millivolts overthe pH range of about 5 to about 9.
17. The process of claim 11 wherein the polymer latex is Chromaset TM 600 surface sizing treatment.
18. The process of claim 11 wherein the treating of step (c) takes place at a size press.
19. The process of claim 11 further comprising adding internal size to the aqueous pulp suspension prior to step (b).
20. The process of claim 19 wherein the internal size is selected from the group consisting of rosin size, ketene dimers, ketene multimers and alkenylsuccinic anhydrides.
21. The process of claim 11 wherein the anionic polymer is in the size composition at a level of about 0.02 wt.% to about 2 wt.% on a dry basis based on the total weight of the size.
22. The process of claim 11 wherein the anionic polymer is in the size composition at a level of about 0.05 wt.% to about 1 wt.% on a dry basis based on the total weight of the size.
23. The process of claim 11 wherein the aqueous size composition further comprises starch.
24. The process of claim 23 wherein the starch in the aqueous size composition is at a level of about 1 wt.% to about 20 wt.% on a dry basis based on the total weight of the aqueous size composition.
25. The process of claim 23 wherein the starch in the aqueous size composition is at a level of about 3 wt.% to about 15 wt.% on a dry basis based on the total weight of the aqueous size composition.
26. The process of claim 23 wherein the starch in the aqueous size composition is at a level of about 5 wt.% to about 10 wt.% on a dry basis based on the total weight of the aqueous size composition.
27. The process of claim 11 wherein the size is applied to paper at a level that provides about 0.02 wt.% to about 0.8 wt.% of the polymer on a dry basis based on the dry weight of the paper.
28. The process of claim 11 wherein the size is applied to paper at a level that provides about 0.05 wt.% to about 0.5 wt.% of the polymer on a dry basis based on the dry weight of the paper.
29. The process of claim 11 wherein the size is applied to paper at a level that provides about 0.1 wt.% to about 0.3 wt.% of the polymer on a dry basis based on the dry weight of the paper.
30. The process of claim 11 wherein the size is applied at a level that provides about 1 wt.% to about 8 wt.% starch on a dry basis based on the dry weight of the paper.
31. The process of claim 11 wherein the size is applied at a level that provides about 2 wt.% to about 6 wt.% starch on a dry basis based on the dry weight of the paper.
32. The process of claim 11 wherein the size is applied at a level that provides about 3 wt.% to about 5 wt.% starch on a dry basis based on the dry weight of the paper.
33. The process of claim 11 further comprising adding internal size to the aqueous pulp suspension prior to step (b), wherein the treating of step (c) takes place at a size press, and the polymer latex is Chromaset TM 600 surface sizing treatment.
34. The process of claim 33 wherein the size contains about 1% to about 20% by weight of starch and about 0.02% to about 2% by weight of the polymer present in Chromaset TM 600 surface sizing treatment, both on a dry basis, based on the total weight of the size, and wherein the size is applied at a level that provides about 0.02 wt.% to about 0.8 wt.% of the polymer and about 1 wt.% to about 8 wt.% starch on a dry basis, based on the dry weight of the paper.
35. The process of claim 11 wherein the polymer contained in said polymer latex is an anionic copolymer of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid.
36. The process of claim 11 wherein the polymer contained in said polymer latex is an anionic copolymer of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid, wherein the styrene or substituted styrene is selected from the group consisting of styrene, .alpha.-methylstyrene, vinyl toluene and mixtures thereof, wherein the alkyl group of the alkyl acrylate or methacrylate contains from 1 to about 12 carbon atoms and wherein the ethylenically unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid and mixtures thereof.
37. The process of claim 11 wherein the polymer contained in said polymer latex is an anionic copolymer of monomers comprising styrene or substituted styrene, alkyl acrylate or methacrylate and ethylenically unsaturated carboxylic acid, wherein the styrene or substituted styrene is styrene, wherein the alkyl acrylate or methacrylate is selected from the group consisting of methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate and mixtures thereof and wherein the ethylenically unsaturated carboxylic acid is selected from the group consisting acrylic acid and methacrylic acid.
38. Sized paper made by the process of claim 1.
39. Sized paper made by the process of claim 7.
40. Sized paper made by the process of claim 11.
41. Sized paper made by the process of claim 17.
42. The paper of claim 40 that performs better in ink jet printing than does paper that is the same except that it does not contain the size composition, when the printing is evaluated for at least one property selected from the groupconsisting of optical density, feathering, wicking, edge roughness and bleed.
43. The paper of claim 40 that has better toner adhesion than does paper that is the same except that it does not contain the size composition.
44. The paper of claim 41 that performs better in ink jet printing than does paper that is the same except that it does not contain the size composition, when the printing is evaluated for at least one property selected from the groupconsisting of optical density, feathering wicking, edge roughness and bleed.
45. The paper of claim 41 that has better toner adhesion than does paper that is the same except that it does not contain the size composition.
46. The paper of claim 40 that has a higher level of sizing than does paper that is the same except that it does not contain the size composition.
47. The paper of claim 41 that has a higher level of sizing than does paper that is the same except that it does not contain the size composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/847,841 US6051107A (en) | 1997-04-28 | 1997-04-28 | Process for surface sizing paper and paper prepared thereby |
| US08/847,841 | 1997-04-28 | ||
| PCT/US1998/006472 WO1998049397A1 (en) | 1997-04-28 | 1998-03-31 | Process for surface sizing paper and paper prepared thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2261602A1 true CA2261602A1 (en) | 1998-11-05 |
Family
ID=25301643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002261602A Abandoned CA2261602A1 (en) | 1997-04-28 | 1998-03-31 | Process for surface sizing paper and paper prepared thereby |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6051107A (en) |
| EP (1) | EP0909355A1 (en) |
| CN (1) | CN1231008A (en) |
| AU (1) | AU728972B2 (en) |
| CA (1) | CA2261602A1 (en) |
| NZ (1) | NZ333948A (en) |
| TW (1) | TW533254B (en) |
| WO (1) | WO1998049397A1 (en) |
| ZA (1) | ZA983545B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143113A (en) * | 1998-03-02 | 2000-11-07 | Le Groupe Recherche I.D. Inc. | Repulpable corrugated boxboard |
| US6764726B1 (en) * | 1999-05-12 | 2004-07-20 | Sen Yang | Ink jet recording sheet with improved image waterfastness |
| CN100439426C (en) * | 1999-05-28 | 2008-12-03 | 株式会社铃木拉特克斯 | Nontacky latex products |
| US6414055B1 (en) | 2000-04-25 | 2002-07-02 | Hercules Incorporated | Method for preparing aqueous size composition |
| US6291127B1 (en) | 2000-08-23 | 2001-09-18 | Eastman Kodak Company | Water-borne polyester coated imaging member |
| US6734232B2 (en) | 2002-03-15 | 2004-05-11 | Georgia-Pacific Resins, Inc. | Styrene-acrylate copolymer composition suitable for surface size |
| US20060009573A1 (en) * | 2002-10-04 | 2006-01-12 | Henk Jan Frans Van Den Abbeele | Aqueous polymer dispersion, preparation and use thereof |
| US20040065425A1 (en) * | 2002-10-07 | 2004-04-08 | Kemira Chemicals, Inc. | Latex paper sizing composition |
| CN1795307B (en) * | 2003-04-07 | 2010-09-08 | 国际纸业公司 | Papers for liquid electrophotographic printing and method for making same |
| US20050022956A1 (en) * | 2003-07-29 | 2005-02-03 | Georgia-Pacific Resins Corporation | Anionic-cationic polymer blend for surface size |
| KR101117020B1 (en) | 2006-10-27 | 2012-03-22 | 크레인 앤드 캄파니 인코퍼레이티드 | A soil and/or moisture resistant secure document |
| US20080163993A1 (en) * | 2007-01-10 | 2008-07-10 | Varnell Daniel F | Surface sizing with sizing agents and glycol ethers |
| KR20140106644A (en) | 2011-12-06 | 2014-09-03 | 바스프 에스이 | Paper and cardboard packaging with barrier coating |
| CN103665244B (en) * | 2013-11-25 | 2016-04-06 | 康吉诺（北京）科技有限公司 | A kind of preparation method of new network IPN coating emulsion and application |
| US10717857B2 (en) | 2015-11-19 | 2020-07-21 | Basf Se | Ammonia-based, imide-containing resin cuts of styrene-maleic resins |
| CN106274120A (en) * | 2016-08-17 | 2017-01-04 | 安徽文峰特种纸业有限公司 | A kind of preferable printing paper of solid color and preparation method thereof |
| CN109137609A (en) * | 2018-07-20 | 2019-01-04 | 蚌埠市奥特纸箱机械有限公司 | A method of improving corrugated paper ring Asia intensity |
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|---|---|---|---|---|
| US2790735A (en) * | 1955-01-31 | 1957-04-30 | Rohm & Haas | Coated paper products and methods of making them |
| US2856310A (en) * | 1955-02-15 | 1958-10-14 | Hercules Powder Co Ltd | Stable ketene dimer-emulsifier mixtures and their preparation |
| NL131880C (en) * | 1958-12-24 | |||
| NL127106C (en) * | 1959-04-23 | 1900-01-01 | ||
| US3242121A (en) * | 1961-05-17 | 1966-03-22 | Union Carbide Corp | Method of preparing latex binder of styrene, an alkyl acrylate, and an ethylenically unsaturated carboxylic acid |
| BE639425A (en) * | 1962-11-02 | 1900-01-01 | ||
| NL6513811A (en) * | 1965-10-26 | 1967-04-27 | ||
| FR2087531A5 (en) * | 1970-05-22 | 1971-12-31 | Ugine Kuhlmann | |
| GB1373788A (en) * | 1971-10-20 | 1974-11-13 | Hercules Powder Co Ltd | Sizing method and composition for use therein |
| DE2228515B1 (en) * | 1972-06-12 | 1974-02-14 | Röhm GmbH, 6100 Darmstadt | METHOD FOR PRODUCING POLYACRYLATE DISPERSIONS |
| FR2270372B1 (en) * | 1974-03-11 | 1976-10-08 | Ugine Kuhlmann | |
| US4040900A (en) * | 1974-05-20 | 1977-08-09 | National Starch And Chemical Corporation | Method of sizing paper |
| GB1533434A (en) * | 1976-03-10 | 1978-11-22 | Hercules Inc | Sizing method and a sizing composition for use therein |
| US4279794A (en) * | 1979-04-26 | 1981-07-21 | Hercules Incorporated | Sizing method and sizing composition for use therein |
| DE3103917A1 (en) * | 1981-02-05 | 1982-08-19 | Bayer Ag, 5090 Leverkusen | CATIONIC SIZING AGENT FOR PAPER AND METHOD FOR THE PRODUCTION THEREOF |
| US4521494A (en) * | 1982-06-03 | 1985-06-04 | The Dow Chemical Company | Styrene-acrylic latex containing a hetero-unsaturated monomer and paper-coating compositions produced therefrom |
| US4464524A (en) * | 1983-07-26 | 1984-08-07 | The Sherwin-Williams Company | Polymeric thickeners and coatings containing same |
| DE3401573A1 (en) * | 1984-01-18 | 1985-07-25 | Bayer Ag, 5090 Leverkusen | CATIONIC SIZING AGENT FOR PAPER AND METHOD FOR THE PRODUCTION THEREOF |
| US4898787A (en) * | 1987-07-02 | 1990-02-06 | Mobil Oil Corporation | Emulsion polymerized cohesive polymer latex useful as cold seal coating and improved sealable articles treated with the same |
| ATE99708T1 (en) * | 1989-07-05 | 1994-01-15 | Giulini Chemie | NEW PAPER SIZES CONTAINING CATIONIC DISPERSING AGENTS. |
| JP3053109B2 (en) * | 1990-11-30 | 2000-06-19 | 三菱製紙株式会社 | Transfer paper for electrophotography |
| DE4133123A1 (en) * | 1991-10-05 | 1993-04-08 | Basf Ag | USE OF COPOLYMERISATES FROM LONG-CHAIN OLEFINS AND MALEINIC ACID ANHYDRIDE IN THE FORM OF HALBAMIDES WITH MORPHOLINE AS A SIZING AGENT FOR PAPER |
| US5663224A (en) * | 1991-12-03 | 1997-09-02 | Rohm And Haas Company | Process for preparing an aqueous dispersion |
| JP2927377B2 (en) * | 1992-08-07 | 1999-07-28 | 日本製紙株式会社 | Ink jet recording paper and method for manufacturing the same |
| GB9311944D0 (en) * | 1993-06-10 | 1993-07-28 | Hercules Inc | Synthesis of alkyl ketene multimers (akm) and application for precision converting grades of fine paper |
| US5685815A (en) * | 1994-02-07 | 1997-11-11 | Hercules Incorporated | Process of using paper containing alkaline sizing agents with improved conversion capability |
| JPH08246391A (en) * | 1994-12-22 | 1996-09-24 | Arakawa Chem Ind Co Ltd | Surface sizing agent for papermaking |
| US5591489A (en) * | 1995-05-04 | 1997-01-07 | Sequa Chemicals, Inc. | Process for surface sizing paper or paperboard |
| BR9611980A (en) * | 1995-12-05 | 1999-02-17 | Dow Chemical Co | Method for externally sizing a fibrous material |
| JPH1046490A (en) * | 1996-07-25 | 1998-02-17 | Mitsui Petrochem Ind Ltd | Composition for coated paper |
-
1997
- 1997-04-28 US US08/847,841 patent/US6051107A/en not_active Expired - Lifetime
-
1998
- 1998-03-31 AU AU68774/98A patent/AU728972B2/en not_active Ceased
- 1998-03-31 EP EP98914414A patent/EP0909355A1/en not_active Withdrawn
- 1998-03-31 CA CA002261602A patent/CA2261602A1/en not_active Abandoned
- 1998-03-31 WO PCT/US1998/006472 patent/WO1998049397A1/en not_active Application Discontinuation
- 1998-03-31 NZ NZ333948A patent/NZ333948A/en unknown
- 1998-03-31 CN CN98800886A patent/CN1231008A/en active Pending
- 1998-04-23 TW TW087106245A patent/TW533254B/en active
- 1998-04-28 ZA ZA983545A patent/ZA983545B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU6877498A (en) | 1998-11-24 |
| AU728972B2 (en) | 2001-01-25 |
| EP0909355A1 (en) | 1999-04-21 |
| NZ333948A (en) | 2000-07-28 |
| WO1998049397A1 (en) | 1998-11-05 |
| TW533254B (en) | 2003-05-21 |
| US6051107A (en) | 2000-04-18 |
| ZA983545B (en) | 1998-10-28 |
| CN1231008A (en) | 1999-10-06 |
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| EEER | Examination request | ||
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